Compound-specific chlorine isotope ratios of TCE,PCE and DCE isomers by direct injection using CF-IRMS

A method for determining compound-specific Cl isotopic compositions (δ³⁷Cl) was developed for tetrachloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cis-DCE), trans-dichloroethene (trans-DCE) and 1,1-dichloroethene (1,1-DCE). The isotope ratio mass spectrometry (IRMS) used in this study has nine collectors, including two for m/z 50 and 52 (CH₃Cl) and two for m/z 94 and 96 (CH₃Br). The development of this method is based on the fact that fragments with mass ratios of 94/96, 95/97 and 96/98 are produced from PCE, TCE and DCE isomers during ion bombardment in the source of a mass spectrometer. Using continuous flow isotope ratio mass spectrometry coupled with gas chromatography (GC–CF-IRMS), it is possible to separate these compounds on-line and directly measure the Cl isotopic ratios of the fragments with the specific mass ratios.Both pure phase and aqueous samples were used for Cl isotopic analysis. For pure phase samples, a vapour phase of the chlorinated ethenes was injected directly into the GC, whereas the solid phase micro extraction (SPME) method was used to extract these compounds from aqueous solutions. The precisions of this analytical technique were ±0.12‰ (1σ, n = 30), ±0.06‰ (1σ, n = 30), and ±0.08‰ (1σ, n = 15) for PCE, TCE and DCE isomers, respectively. The limits of quantification (LOQ) for analyzing Cl isotopic composition in aqueous solutions were 20, 5, and 5 μg/L for PCE, TCE and DCE isomers, respectively. This corresponds to 6–9 nano-mole of Cl, which is approximately 80 times lower than the most sensitive existing method. Compared to methods previously available, this new development offers the following advantages: (1) The much lower LOQ make it possible to extract these compounds directly from aqueous solutions using SPME without pre-concentration; (2) The linking of a GC with an IRMS eliminates off-line separation; and (3) Because the fragments used for isotopic ratio measurement are produced during ion bombardment in the mass spectrometer, there is no need to convert chlorinated ethenes to methyl chloride. As a result, this technique greatly enhances the efficiency for isotopic analysis by eliminating procedures for pre-concentration, off-line separation and sample preparation. In addition, it also reduces the potential for isotopic fractionation introduced during these procedures.Compound-specific Cl stable isotope analysis can be used as a tool to study the sources of organic contaminants in groundwater and their behaviour in the subsurface environments. It may also assist in understanding processes such as transport, mixing, and degradation reactions.     

苯、甲苯对粒状铁去除四氯乙烯影响的柱实验研究

挥发性氯代烃和石油烃类污染是地下水中最常见的混合污染类型,而且这两类污染物毒性极强,对人类危害非常严重。文中选取具有代表性的四氯乙烯、苯和甲苯为研究对象,采用柱实验的方法研究苯和甲苯在粒状铁反应系统中吸附平衡后,对粒状铁去除四氯乙烯的机理及反应动力学的影响。在实验装置运行的过程中,苯、甲苯和四氯乙烯的浓度始终控制在2mg/L左右的水平。实验结果表明:苯或甲苯的存在对被还原的产物组成没有影响,主要氯代中间产物均为TCE、1,1-DCE、cis-1,2-DCE和VC,但组成比例略有不同。苯和甲苯的存在对去除速率有影响,即苯对四氯乙烯的去除有促进作用,去除速率平均提高13.5%;而甲苯则抑制四氯乙烯的去除,去除速率平均降低13.8%。对比控制柱,苯和甲苯存在时对出水水化学变化的影响没有明显差异。     

Remediation of ground water containing chlorinated and brominated hydrocarbons, benzene and chromate by sequential treatment using ZVI and GAC

A laboratory experiment with two sequenced columns was performed as a preliminary study for the installation of a permeable reactive barrier (PRB) at a site where a mixed ground water contamination exists. The first column contained granular zero valent iron (ZVI), the second column was filled with granular activated carbon (GAC). Trichloromethane (TCM, 930 μg/l) and chlorobenzene (MCB, 260 μg/l) were added to the ground water from the site as the main contaminants. Smaller amounts (<60 μg/l) of benzene, 1,2-dichloroethane, 1,1,2-trichloroethane (1,1,2-TCA), 1,1-dichloroethene (1,1-DCE), trichloroethene (TCE), tetrachloroethene (PCE), 1,2-dichloropropane (1,2-DCP), bromodichloromethane (BDCM), dibromochloromethane (DBCM), tribromomethane (TBM), vinyl chloride and chromate were also added to the water to simulate the complex contamination pattern at the site of interest. PCE, TCE, 1,1-DCE, DBCM, BDCM, TBM, MCB and chromate were remediated in contact with ZVI, while the remaining contaminants showed incomplete degradation. A fraction of 8–16.5% TCM was converted to dichloromethane (DCM). Remaining contaminant concentrations were efficiently sorbed by the GAC until breakthrough of DCM was observed after 1,230 exchanged pore volumes in the GAC. The results show that the complex mixture of contaminants can be remediated by a sequenced PRB consisting of ZVI and GAC and that DCM sorption capacity is the critical parameter for the dimensions of the GAC reactor.     

Products of abiotic U(VI) reduction by biogenic magnetite and vivianite

Reductive immobilization of uranium by the stimulation of dissimilatory metal-reducing bacteria (DMRB) has been investigated as a remediation strategy for subsurface U(VI) contamination. In those environments, DMRB may utilize a variety of electron acceptors, such as ferric iron which can lead to the formation of reactive biogenic Fe(II) phases. These biogenic phases could potentially mediate abiotic U(VI) reduction. In this work, the DMRB Shewanella putrefaciens strain CN32 was used to synthesize two biogenic Fe(II)-bearing minerals: magnetite (a mixed Fe(II)-Fe(III) oxide) and vivianite (an Fe(II)-phosphate). Analysis of abiotic redox interactions between these biogenic minerals and U(VI) showed that both biogenic minerals reduced U(VI) completely. XAS analysis indicates significant differences in speciation of the reduced uranium after reaction with the two biogenic Fe(II)-bearing minerals. While biogenic magnetite favored the formation of structurally ordered, crystalline UO₂, biogenic vivianite led to the formation of a monomeric U(IV) species lacking U-U associations in the corresponding EXAFS spectrum. To investigate the role of phosphate in the formation of monomeric U(IV) such as sorbed U(IV) species complexed by mineral surfaces, versus a U(IV) mineral, uranium was reduced by biogenic magnetite that was pre-sorbed with phosphate. XAS analysis of this sample also revealed the formation of monomeric U(IV) species suggesting that the presence of phosphate hinders formation of UO₂. This work shows that U(VI) reduction products formed during in situ biostimulation can be influenced by the mineralogical and geochemical composition of the surrounding environment, as well as by the interfacial solute-solid chemistry of the solid-phase reductant.     

Calculation of pH and mineral equilibria in hydrothermal waters with application to geothermometry and studies of boiling and dilution

Using chemical analyses and 25° pH measurements of quenched high-temperature waters, we calculate in situ pH and distribution of aqueous species at high temperature. This is accomplished by solving simultaneous mass action equations for complexes and redox equilibria and mass balance equations, on all components, including a H⁺ equation with as many as 60 terms (depending on water composition). This calculation provides accurate values for the activities of aqueous ions in a given water at high temperature, which are used to calculate an ion activity product (Q) for each of more than 100 minerals. The value of log(Q/K) for each mineral, where K is the equilibrium constant, provides a measure of proximity of the aqueous solution to equilibrium with the mineral. By plotting log Q/Kvs. T for natural waters, it is possible to determine: a) whether the water was in equilibrium with a host rock mineral assemblage, b) probable minerals in the equilibrium assemblage and c) the temperature of equilibrium. In cases where the fluid departs from equilibrium with a host rock assemblage, it is possible to determine whether this may result from boiling or dilution, and an estimate of amount of lost gas or diluting water can be determined.The calculation is illustrated by application to geothermal waters from Iceland, Broadlands, and Sulphur Bank, hot spring waters from Jemez, Yellowstone and Blackfoot Reservoir (Idaho) and fluid inclusions from the Sunnyside Mine, Colorado. It is shown that most geothermal waters approach equilibrium with a subsurface mineral assemblage at a temperature close to measured temperatures and that some hot springs also approach equilibrium with the host rock at temperatures above outlet temperatures but commonly below the Na-K-Ca temperatures. The log Q/K plots show that some discrepancies between Na-K-Ca temperatures on spring waters and actual temperatures result from a failure of alkali feldspars to equilibrate with the fluid and with each other.Calculations on Sulphur Bank fluids show that boiling probably caused cinnabar precipitation near 150°C and that the boiled fluids equilibrated with secondary minerals near 150° even though temperatures up to 185° have been measured at depth. For the fluid inclusions, the measured bubble temperatures are close to those calculated for equilibration of the fluid with the observed sulfide mineral assemblage.New estimates of stability constants for aluminum hydroxide complexes are included at the end of the paper.     

Calculation of the standard partial molal thermodynamic properties and dissociation constants of aqueous HCl0 and HBr0 at temperatures to 1000°C and pressures to 5 kbar

Dissociation constants of aqueous ion pairs HCl⁰ and HBr⁰ derived in the literature from vapor pressure and supercritical conductance measurements Quist and Marshall 1968b, Frantz and Marshall 1984 were used to calculate the standard partial molal thermodynamic properties of the species at 25°C and 1 bar. Regression of the data with the aid of revised Helgeson-Kirkham-Flowers equations of state Helgeson et al 1981, Tanger 1988, Shock et al 1989 resulted in a set of equations-of-state parameters that permits accurate calculation of the thermodynamic properties of the species at high temperatures and pressures. These properties and parameters reproduce generally within 0.1 log unit (with observed maximum deviation of 0.23 log unit) the log K values for HBr⁰ and HCl⁰ given by Quist and Marshall (1968b) and Frantz and Marshall (1984), respectively, at temperatures to 800°C and pressures to 5 kbar.     

The role of prokaryotes in subsurface weathering of hydrothermal sediments: A combined geochemical and microbiological investigation

A detailed geochemical and microbiological study of a ∼2 m sediment core from the inactive Alvin mounds within the TAG hydrothermal field was conducted to examine, for the first time, the role of prokaryotes in subsurface weathering of hydrothermal sediments. Results show that there has been substantial post-depositional remobilisation of metal species and diagenetic overprinting of the original high-temperature hydrothermal minerals, and aspects have involved prokaryotic processes. Prokaryotic enumeration demonstrates the presence of a population smaller than the average for deep sea sediments, probably due to the low organic carbon content, but not inhibited by (and hence adapted to) the metal rich environment. There was a small but significant increase in population size associated with the active redox boundary in an upper metal sulphide layer (50-70 cm) around which active metal remobilisation was concentrated (Cu, Au, Cd, Ag, U, Zn and Zn). Hence, subsurface prokaryotes were potentially obtaining energy from metal metabolism in this near surface zone. Close association of numbers of culturable Mn and Fe reducing prokaryotes with subsurface Fe²⁺ and Mn²⁺ pore water profiles suggested active prokaryotic metal reduction at depth in core CD102/43 (to ∼175 cm). In addition, a prokaryotic mechanism, which is associated with bacterial sulphate reduction, is invoked to explain the U enrichment on pyrite surfaces and Zn and Pb remobilisation in the upper sediment. Although prokaryotic populations are present throughout this metalliferous sediment, thermodynamic calculations indicated that the inferred low pH of pore waters and the suboxic/anoxic conditions limits the potential energy available from Fe(II) oxidation, which may restrict prokaryotic chemolithotrophic biomass. This suggests that intense prokaryotic Fe oxidation and weathering of seafloor massive sulphide deposits may be restricted to the upper portion of the deposit that is influenced by near neutral pH and oxic seawater unless there is significant subsurface fluid flow.     

Experimental studies of the distribution of rare earths as trace elements among silicate minerals and liquids and water

The distribution of the REE between synthetic diopside, forsterite, enstatite, and gaseous water and between natural plagioclase, 2 rhyolite obsidian melts and gaseous water have been measured. Values for distribution coefficients (D) for the REE between the minerals and aqueous fluid vary significantly over the temperature range of 550°C to 850°C, but little variation was found for the values of D between the silicate liquids and aqueous fluid over a temperature range of 100°C. By assuming that the values of D for the silicate liquids are independent of major element composition and temperature, it is possible to calculate values of D for REE between silicate minerals and silicate liquid. The values obtained for diopside, forsterite, enstatite and plagioclase compare favorably with those obtained for the natural materials clinopyroxene, olivine, orthopyroxene and plagioclase (except for Eu). The values of D for diopside were found to increase and those for forsterite and enstatite to decrease with increasing temperatuie. Values of temperature of equilibration for natural minerals obtained by extrapolation of graphs for experimental data of In D against 1/T for the systems diopside-silicate liquid, forsterite-silicate liquid, and forsterite-diopside fall within a reasonable range, suggesting the possibility of geothermometry using REE concentrations of minerals.     

Theoretical modelling of cis -vacant and trans -vacant configurations in the octahedral sheet of illites and smectites

 The cis-vacant configurations of smectites and illites have been studied theoretically by using transferable empirical interatomic potentials. A wide range of compositions of octahedral and tetrahedral cation and interlayer charge has been considered. All results have been compared with the trans-vacant configurations in each sample. The calculated values reproduce the differences in the lattice parameters between the cis- and trans-vacant configurations of experimental studies. Taking into account the cis-/trans-vacant proportion, the calculated structures agree with experiment for the main structural features of the crystal lattice. The effect of the cation substitution in the octahedral and tetrahedral sheets on the cell parameters has been also studied, finding good linear relationships. The calculated cation substitution effects are consistent with experimental results. Although the energy difference between the cis- and trans-vacant configurations is small, the cis-vacant is more stable when the composition of clays is more smectitic, like the experimental behaviour. Similar trends of the cation substitution effect on the cis-/trans-vacant proportion to the experimental results are found. The structure of the hydroxy groups has also been analysed. The OH bond length, the orientation of the O–H bond with respect to the (001) plane and the non-bonding H...O distances have been studied. Received: 4 September 2000 / Accepted: 29 January 2001     

Mineral-solution equilibria—V. Solubilities of rock-forming minerals in supercritical fluids

The solubility constants of sixty-nine rock-forming minerals have been computed for temperatures between 400 and 600°C at 1000 and 2000 bar pressure using the free-energy data for aqueous solutes presented in Parts I through IV of this series combined with the thermodynamic properties of minerals from Helgesonet al. (1978). An example describing solution compositions in equilibrium with a spilite is discussed. A computer program for calculating solution compositions in equilibrium with mineral assemblages is included as an appendix.     

A new simple approach to evaluate pedogenic clay transformation in a Vertic Calcisol

The aim of this study is to characterize the pedogenic clay minerals by using simple approach: mixing mineralogical and geochemical findings.The fine clay fractions (< 0.1 μm) of a Vertic Cambisol profile were studied by means of X-ray diffraction (XRD), infrared spectroscopy (FTIR) and cation exchange capacity (CEC).Qualitative and quantitative mineralogical compositions of the clay mixture were determined.Moreover, chemical equilibria and thermodynamic stabilities of minerals (calcite, gypsum, kaolinite, smectites and illites) were studied using results of ionic activities obtained from total concentration of various aqueous species in water extracts from soil-saturated pastes.XRD analysis shows a good homogeneity in the mineralogical composition of the soil material, with depth of soil profiles. The identified clay minerals are mainly illite–smectite mixed layers (I/S) and kaolinite. The chemical analysis of saturated paste extracts with clay minerals shows a slight undersaturation of the illitic phase while smectites and also calcite and gypsum reach the thermodynamic equilibrium along the soil profile.     

负载型纳米Pd/Fe对挥发性氯代烃的去除

氯代烃的污染治理已成为当今世界最热门的研究领域之一。以水体中最常见的氯代烃污染物1,1-二氯乙烯（1,1-DCE）、林丹（γ-HCH）为主要目标污染物,探讨了不同条件下负载型纳米Pd/Fe对氯代烃的去除效果。负载型纳米Pd/Fe采用浸渍→液相还原→还原沉淀的方法制备,透射电镜显示采用该方法制备的负载型金属钯和铁的平均粒径均在纳米级范围内。负载型纳米Pd/Fe具有较高的表面反应活性,当负载型纳米Pd/Fe 用量为40 g/L、反应时间达2 h时,1.1-二氯乙烯和林丹的去除率分别达到85%和100%。脱氯率与Pd/Fe投加量、钯含量、初始pH值、反应温度等因素有关,与溶液的初始浓度关系不大。负载型纳米Pd/Fe对11-DCE和γ-HCH去除均符合一级反应动力学方程,速率常数分别为0-528 3 h^-1及2-012 9 h^-1,反应的半衰期t1/2分别为1.31 h和0.34 h。推断在反应过程中,Fe腐蚀产生的H2为主要还原剂,Pd是良好的加氢催化剂,在金属颗粒表面形成高浓度反应相,使反应短时间内完成。     

Thermodynamic description of aqueous nonelectrolytes at infinite dilution over a wide range of state parameters

A new, virial-like equation of state (EoS) for describing the thermodynamic properties of aqueous nonelectrolytes at infinite dilution is proposed. It is based on the accurate EoS for a solvent (H₂O) given by Hill (1990) and requires only three empirical parameters to be fitted to experimental data, and these are independent of temperature and pressure. Knowledge of the thermodynamic properties of a pure gas, together with these three parameters, enables prediction of the whole set thermodynamic properties of the solute at infinite dilution (chemical potential, entropy, molar volume, and apparent molar heat capacity) over a wide range of temperatures (0 to 500°C) and pressures (1 to 2000 bars), including the near-critical region. In the cases in which experimental thermodynamic data are lacking, the empirical parameters can be estimated solely from the known standard-state properties of the solute. The new EoS is compatible with the Helgeson-Kirkham-Flowers model for aqueous electrolytes, and thus it can be applied to reactions involving minerals, gases, and aqueous ions, in addition to uncharged species.     

The thermodynamic properties of radium

The enthalpy, Gibbs free energy, and entropies of aqueous radium species and radium solids have been evaluated from empirical data, or estimated when necessary for 25°C and 1 bar. Estimates were based on such approaches as extrapolation of the thermodynamic properties of Ca, Sr, and Ba complexes and solids plotted against cationic radii and charge to radius functions, and the use of the Fuoss or electrostatic mathematical models of ion pair formation (Langmuir, 1979). Resultant log K (assoc) and ΔH⁰ (assoc) (kcal/mol) values are: for RaOH⁺ 0.5 and 1.1; RaCl⁺ ?0.10 and 0.50; RaCO⁰₃ 2.5 and 1.07; and RaSO⁰₄ 2.75 and 1.3. Log Ksp and ΔH⁰ (dissoc) (kcal/mol) values for RaCO₃(c) and RaSO₄(c) are ?8.3 and ?2.8, and ?10.26 and ?9.4, respectively.Trace Ra solid solution in salts of Pb and of the lighter alkaline earths, has been appraised based on published distribution coefficient (D) data, where D ～- (mM²⁺)(N_RaX)/(mRa²⁺)(N_MX) (m and N are the aqueous molality and mole fraction of Ra and cation M in salt X, respectively. The empirical solid solution data have been used to derive both enthalpies and Gibbs free energies of solid solution of trace Ra in sulfate and carbonate minerals up to 100°C. Results show that in every case D values decrease with increasing temperature. Among the sulfate and carbonate minerals, D values decrease for the following minerals in the order: anhydrite > celestite > anglesite > barite > aragonite > strontianite > witherite > cerussite.     

Carboxylic acid anions in formation waters,San Joaquin Basin and Louisiana Gulf Coast,U.S.A.—Implications for clastic diagenesis. Reply to discussion by P.D. Lundegard and L.S. Land

MacGowan and Surdam (1990a) suggested some modifications to the model of Lundegard and Land (1989) to make it more geologically and geochemically reasonable. The predictive power of such a geochemical model is wholly dependent on the species modeled and the constants used; any model that excludes important species or important thermodynamic data, or one that couples certain reactions in an unrealistic way, may produce results which are not geologically or geochemically reasonable (W. K. Harrison, pers. commun., 1988; Y. K. Kharaka, pers. commun., 1991). We have long recognized that, under early-burial diagenetic conditions, aluminosilicate hydrolysis generally controls formation water pH (Surdam and Eugster, 1976; Mariner and Surdam, 1970; Taylor and Surdam, 1981) and that, during intermediate burial, either aqueous CO₂ or CAA species (in the absence of aqueous S species or other weak conjugate acid-base pairs) will dominate formation water alkalinity and control pH (Surdam et al., 1989c). We reassert that the model of Lundegard and Land (1989) does not take into account the relative importance of PCO₂ and of concentrations of both Ca²⁺ and CAA and their relative organic metal complexes to carbonate mineral stability in sandstones in the zone of intermediate burial clastic diagenesis (cf. the models of Surdam et al., 1984 and Surdam and Crossey, 1985). The usefulness of such models is predicted on the completeness of the model and the use of the best, most accurate thermodynamic data. Also, geologically realistic concentrations of critical species are required for reasonable modeling to be done. Although their model is vigorously defended in the discussion of Lundegard and Land, 1989, Lundegard and Land, 1993, we continue to disagree that their analysis of their model conditions are either geologically or geochemically satisfying.We agree with the fundamental approach and philosophy of Lundegard and Land, 1989, Lundegard and Land, 1993. It is of the utmost importance to determine from experimental, geochemical, petrographic, and geological data what the controls on pH and alkalinity in formation waters are, as well as the exact thermodynamic speciation of aqueous moieties and the stability of detrital and authigenic minerals. Lundegard and Land (1993) raise an additional point about CAA reaction with carbonate minerals in shales, although Fisher and Lewan (1989), Lewan (1989) and MacGowan and Surdam (1990b) have demonstrated that CAA generated in shale likely migrate in the oil phase along incipient shale microfractures to the sandstone reservoir, and thus are likely to not react much with the shale. Finally, we agree with Lundegard and Land that these areas require much additional experimental and field analysis, and petrographic study.     

Timescales of interface-coupled dissolution-precipitation reactions on carbonates

In the Earth's upper crust, where aqueous fluids can circulate freely, most mineral transformations are controlled by the coupling between the dissolution of a mineral that releases chemical species into the fluid and precipitation of new minerals that contain some of the released species in their crystal structure, the coupled process being driven by a reduction of the total free-energy of the system. Such coupled dissolution-precipitation processes occur at the fluid-mineral interface where the chemical gradients are highest and heterogeneous nucleation can be promoted, therefore controlling the growth kinetics of the new minerals. Time-lapse nanoscale imaging using Atomic Force Microscopy (AFM) can monitor the whole coupled process under in situ conditions and allow identifying the time scales involved and the controlling parameters. We have performed a series of experiments on carbonate minerals (calcite, siderite, dolomite and magnesite) where dissolution of the carbonate and precipitation of a new mineral was imaged and followed through time. In the presence of various species in the reacting fluid (e. g. antimony, selenium, arsenic, phosphate), the calcium released during calcite dissolution binds with these species to form new minerals that sequester these hazardous species in the form of a stable solid phase. For siderite, the coupling involves the release of Fe²⁺ ions that subsequently become oxidized and then precipitate in the form of Fe^III oxyhydroxides. For dolomite and magnesite, dissolution in the presence of pure water (undersaturated with any possible phase) results in the immediate precipitation of hydrated Mg-carbonate phases. In all these systems, dissolution and precipitation are coupled and occur directly in a boundary layer at the carbonate surface. Scaling arguments demonstrate that the thickness of this boundary layer is controlled by the rate of carbonate dissolution, the equilibrium concentration of the precipitates and the kinetics of diffusion of species in a boundary layer. From these parameters a characteristic time scale and a characteristic length scale of the boundary layer can be derived. This boundary layer grows with time and never reaches a steady state thickness as long as dissolution of the carbonate is faster than precipitation of the new mineral. At ambient temperature, the surface reactions of these dissolving carbonates occur on time-scales of the order of seconds to minutes, indicating the rapid surface rearrangement of carbonates in the presence of aqueous fluids. As a consequence, many carbonate-fluid reactions in low temperature environments are controlled by local thermodynamic equilibria rather than by the global equilibrium in the whole system.     

Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments

Sunlight-induced reduction and dissolution of colloidal Fe-Mn (hydr)oxide minerals yields elevated concentrations of Fe²⁺ and Mn²⁺ in natural waters. Since these elements may be biolimiting micronutrients, photochemical reactions might play a significant role in biogeochemical cycles. Reductive photodissolution of Fe (hydr)oxide minerals may also release sorbed metals. The reactivity of Fe-Mn (hydr)oxide minerals to sunlight-induced photochemical dissolution is determined by the electronic structure of the mineral-water interface. In this work, oxygen K-edge absorption and emission spectra were used to determine the electronic structures of iron(III) (hydr)oxides (hematite, goethite, lepidocrocite, akaganeite and schwertmannite) and manganese(IV) oxides (pyrolusite, birnessite, cryptomelane). The band gaps in the iron(III) (hydr)oxide minerals are near 2.0-2.5 eV; the band gaps in the manganese (IV) oxide phases are 1.0-1.8 eV. Using published values for the electrochemical flat-band potential for hematite together with experimental pH_pzc values for the (hydr)oxides, it is possible to predict the electrochemical potentials of the conduction and valence bands in aqueous solutions as a function of pH. The band potentials enable semiquantitative predictions of the susceptibilities of these minerals to photochemical dissolution in aqueous solutions. At pH 2 (e.g., acid-mine waters), photoreduction of iron(III) (hydr)oxides could yield millimolal concentrations of aqueous Fe²⁺ (assuming surface detachment of Fe²⁺ is not rate limiting). In seawater (pH 8.3), however, the direct photo-reduction of colloidal iron(III) (hydr)oxides to give nanomolal concentrations of dissolved, uncomplexed, Fe²⁺ is not thermodynamically feasible. This supports the hypothesis that the apparent photodissolution of iron(III) (hydr)oxides in marines systems results from Fe³⁺ reduction by photochemically produced superoxide. In contrast, the direct photoreduction of manganese oxides should be energetically feasible at pH 2 and 8.3.     

Fate and transport of metals in H2S-rich waters at a treatment wetland

The aqueous geochemistry of Zn, Cu, Cd, Fe, Mn and As is discussed within the context of an anaerobic treatment wetland in Butte, Montana. The water being treated had a circum-neutral pH with high concentrations of trace metals and sulfate. Reducing conditions in the wetland substrate promoted bacterial sulfate reduction (BSR) and precipitation of dissolved metal as sulfide minerals. ZnS was the most common sulfide phase found, and consisted of framboidal clusters of individual spheres with diameters in the submicron range. Some of the ZnS particles passed through the subsurface flow, anaerobic cells in suspended form. The concentration of "dissolved" trace metals (passing through a 0.45 μm filter) was monitored as a function of H₂S concentration, and compared to predicted solubilities based on experimental studies of aqueous metal complexation with dissolved sulfide. Whereas the theoretical predictions produce "U-shaped" solubility curves as a function of H₂S, the field data show a flat dependence of metal concentration on H₂S. Observed metal concentrations for Zn, Cu and Cd were greater than the predicted values, particularly at low H₂S concentration, whereas Mn and As were undersaturated with their respective metal sulfides. Results from this study show that water treatment facilities employing BSR have the potential to mobilize arsenic out of mineral substrates at levels that may exceed regulatory criteria. Dissolved iron was close to equilibrium saturation with amorphous FeS at the higher range of sulfide concentrations observed (>0.1 mmol H₂S), but was more likely constrained by goethite at lower H₂S levels. Inconsistencies between our field results and theoretical predictions may be due to several problems, including: (i) a lack of understanding of the form, valence, and thermodynamic stability of poorly crystalline metal sulfide precipitates; (ii) the possible influence of metal sulfide colloids imparting an erroneously high "dissolved" metal concentration; (iii) inaccurate or incomplete thermodynamic data for aqueous metal complexes at the conditions of the treatment facility; and (iv) difficulties in accurately measuring low concentrations of dissolved sulfide in the field.     

Hydrodynamic and isotopic characterization of a site contaminated by chlorinated solvents: Chienti River Valley,Central Italy

Contaminant sources have been attributed to shoe manufacturers in an alluvial aquifer located along 26 km² in the Chienti River Valley, Central Italy. During the 1980s and 1990s, the main chlorinated compound used in the study area was 1,1,1-Trichloroethane (1,1,1-TCA), which was substituted by Perchloroethene (PCE) in the last 15 years. A hydrogeological conceptual model has been developed for the alluvial aquifer taking into account the presence of low permeability lenses, forming a multilayer semi-confined aquifer. Hydrodynamic tests (pumping and flowmeter heat-pulse tests) coupled with standard and multilevel hydrochemical and isotopic samplings were performed. Flowmeter tests showed the existence of vertical flow between aquifer levels having different permeability. Physical–chemical parameter logs agreed with the existence of a multilayer aquifer. Concentration data collected in 21 wells located downgradient of the different sources revealed VOC (Volatile Organic Compound) levels lower than 100 μg/L in the upper part of the valley and levels reaching about 200 μg/L in the near shore areas. PCE is the main compound present in the aquifer. No evidence of the presence of TCA was found in the upper areas of the Chienti Valley, but in the areas near the shore, TCA and its degradation products are predominant. Data collected at multilevels located at two sites (upper and near shore areas) to refine the results obtained in the regional survey show a stratification of the VOC concentrations; values of each compound are higher than those measured in the conventional wells during the standard sampling (e.g. PCE: 150 μg/L instead of 2 μg/L). In addition, the vertical distribution of the contaminant reflects the vertical flow pattern inferred from hydrogeological data. The hydrogeological, VOC and isotope data showed that dilution is the main process controlling VOCs concentration in the aquifer. Degradation also played a role in the attenuation of the parent compounds in some localized areas of the aquifer. The role of the low permeability layers on VOC degradation was documented by the presence of cis-1,2-DCE, a main daughter product of PCE, in some zones of the upper area, and 1,1-Dichloroethene (1,1-DCE) and 1,1-Dichloroethane (1,1-DCA), byproducts of 1,1,1-TCA degradation, in the near shore areas.